Treatment of hydrocarbons



Get. 1'9,v 1948.

c. BL LINN TREATUENT 0F HYDROGARBOHS K Enea oct. 25.A 1945 t Patented ou. 19, 194s- TREATMENT 'OF HYDROCARBONS Carl B.- Linn, Riverside, Ill., assignor to Universal Oil Products Company, Chicago, lll., a corporation of Delaware application october 25, 1945, seal No. 624,503

This invention relates to a process for treat- 8 Claims. (Cl. 26o-676) ing a hydrocarbon or hydrocarbon mixture which is contaminated by small amountsof organic flu# y orine compounds to remove iluorine therefrom.

More specifically, it relates to the treatment of hydrocarbons produced synthetically in thek presence of an active fluoride catalyst to remove small amounts of organically combined fluorine present in compounds admixed with the hydrocarbon or hydrocarbons.

The invention is particularly adapted to the treatment of hydrocarbons produced by the alkylation of isoparanic hydrocarbons with olenic hydrocarbons or lwith alkyl iluorides using active iluorlde catalysts including hydrogen iluoride or fluoride mixtures-comprising essentially hydrogen iluorid'e and boron fluoride. The process is also applicable to the removal of alkyl iluorides from propane and butane fractions. the latter comprising 'particularly'normal butane recovered from the gaseous products discharged form an alkyiation plant in which a butaneor pentane fraction is alkylated by propylene present in a propanepropylene fraction. l

An object of this invention is to deuorinate a hydrocarbon or hydrocarbon mixture contaminated by relatively small amounts of organic fluorine compounds, particularly alkyl fiuorides.

Another object of this invention is to dehydrofluorinate an isoparaflln alkyiation product formed in the presence of an active fluoride catalyst.

A further object of this-invention is to remove alkyl fluorides from hydrocarbon conversion' products formed in the presence of an active fluoride catalyst. f

A still further object of this invention is to remove alkyl fluorides from a fraction of normally gaseous paraillnlc hydrocarbons recovered vfrom the products formed in the alkyiation of isobutane by olens present in a Cs-C4 hydrocarbon fraction.

Another object of this invention is to remove ethyl uoride from a propane fraction recovered from the products formed in the alkyiation of isobutane in thevpresence of hydrogen fluoride with apropane-propylene fractioncontaining a relatively small amount of ethylene. l

One specific embodiment of the present invention comprises a process for treating hydrocarbon material containing as an impurity a relatively small percentage of organically combined fluorine to remove iluorine therefrom which comprises contacting said material with a mixture of liquid hydrogen fluoride and a hydrogen fluoride sludge resulting from the treatment of hydrocarbons with liquid hydrogen uoride.

Another embodiment of the present invention comprises a process for treating hydrocarbon material containing as an impurity a relatively small percentage of organically. combined fiuorine to remove fluorine therefrom which comprises contacting said material with a mixture of liquid hydrogen fluoride and the organic constituents of a hydrogen fluoride sludge resulting from the treatment of hydrocarbons with liquid hydrogen fluoride.

A further embodiment of the present invention comprises aprocess for treating hydrocarbon material containing as an impurity a relatively small percentage of organically combined iiuorine to remove iluorine therefrom which comprises contacting said material with a mixture of from about 40 to about 90% by volume of liquid hydrogen uorlde and from about 60 to about 10% by volume of the organic constituents of a hydrogen uoride sludge resulting from the treatment of hydrocarbons with liquid hydrogen fluoride.

A still further embodiment comprises a process for treating hydrocarbons recovered from an alkyiation process in which an alkylatable paraflln is alkylated with an olen having at least 3 carbon atoms per molecule in the presence of an active fluoride catalyst by treating said hydrocarbons with a mixture of hydrogen fluoride and the organic constituents of a hydrogen fluoride sludge formed incidental to the alkyiation of. an alkylatable paramn with an olefin in the presence of an active fluoride catalyst comprising hydrogen fluoride.

The alkyiation of branched chain paralnic hydrocarbons such as isobutane and isopentane with olenic hydrocarbons, particularly the olefinic hydrocarbons present in cracked gases, produces saturated liquid hydrocarbons utilizable as constituents of gasoline of high antiknock'value. By this means relatively lowlboilingV isoparaiilnic hydrocarbons are alkylated with low boiling olens and thereby converted into materials of higher boiling point andhigh antiknock values, such hydrocarbonaceous materials being particularly useful as components of aviation gasoline. The

higher boiling hydrocarbons so formed from low boiling isoparamns and oleflns in the presence of an active fluoride catalyst including hydrogen fluoride or mixtures of hydrogen uoride and boron fluoride, frequentlyicontain small amounts of organic iluorine compounds which are not readily removable by washing with caustic and water or by fractional distillation.4 These contaminating `may be encountered in iluorinecompounds which are thus present in hy'- drocarbon mixtures are possibly due to the interaction of hydrogen fluoride with olens to form alkyl fluorides. Some alkyl fluorides are more stable than others in the presenceof active fluoride catalysts. Thus, ethyl fluoride is more stable than thehighermolecular weightalkyl uorides which may occur in an alkylation reaction mixture and is not converted completely into alkylation product but admixes with the hydrocarbon products. Some higher boiling-alkyl iluorides and other organic uorine compounds' may also remain in hydrocarbon alkylation products. Because of its high stability, boiling point, and the fact that it forms with propane an azeotropic mixture boiling at 47 C., ethyl uoride is found in the propane fraction recovered from an alkylation process utilizing a, propane-propylene fraction as an olenic charging stock. Such propanepropylene charging stocks frequently contain ethylene in small amounts and form ethyl fluoride by the addition oflhydrogen fluoride to this olefin of lowest molecular weight. Boron fluoride assists hydrogen fluoride in catalyzing the alkylation of an isoparaln by ethylene and higher olefins, but in these cases the alkylation product also contains small quantities of organic uorides as do those formed similarly in the presence of hydrogen fluoride from an isoparaflin and an olefin of higherpmolecular weight than ethylene.

Although the fluorine content of the hydrocarbon product of gasoline boiling range resulting from an alkylation treatment is rarely very high,

'the presence of fiuorine is undesirable both from the'standpoint that the combustion products of such a fuel are corrosive, as Well as the fact that the antiknock value of the gasoline, generally excovered from the eilluent gases.

pressed by the term octane number is reduced I considerably either when the gasoline is used as such, or when a small amount of an antidetonating agent such as lead tetraethyl is added thereto. T 'hus it may be shown that gasoline fractions containing 0.1% by weight of fluorine have inferlor antiknock properties, particularly as concerns their response to lead tetraethyl as compared to the otherwise same material which contains substantially no iluorine compounds. The

present invention offers a method for reducing the .i uorine contenti of the hydrocarbon alkylation product to an amount where itis no longer objectionable.

Also, propane and normal butane which are not alkylated during the alkylation treatment of an isoparaffin with a C3 or anCi hydrocarbon fracl tion are recovered from alkylation products and used as fuels and for various industrial uses such as in the production of hydrogen. Such recovered propane and normal butane fractions are sometimes contaminated by ethyl fluoride andL other organic uorine compounds formed incidentally in the alkylation treatment and it is desirable that these propane and butane frac- A tions be freed from fluorine compounds before being utilized as above indicated.

It is much more diicult to dehydrofluorinate f ethyl fluoride than-the other alkyl uorides which products of the hydrogen fluoride alkylation process. It has been observed that alkylation plants which charge a propanepropylene feed stock to the alkylation reactor 'produce ethyl fluoride from the ethylene which often contaminates the C3' feed stock. This ethyl fluoride vtends to gothrough the plant unchanged and. finally appears in the propane fraction re- The methods used heretofore for removing organic fiuorine compounds from alkylate such as passage through heated contactors containing bauxite or aluminum do not cause the dehydrofiuorination of. ethyl uoride and consequently are ineffective for producinga propane fraction substantially free fromv fiuorine. lMy process, however, defluorinates not only alkylate but also propane and makes it possible to produce a substantially fluorine-free propane fraction.

As indicated above, ethyl fluoride is more stable than the higher alkyl fluorides encountered in the products of the hydrogen fluoride alkylation process. Possibly one reason for this difference in stability of the alkyl fiuorides is the fact that ethyl fluoride is a primary alkyl fluoride, while the alkyl fiuorides produced from propylene .and higher oleflns are either secondary or tertiary alkyl fluorides. I have found that a relatively large proportion of a hydrogen fluoride sludge resulting from the treatment of hydrocarbons with liquid hydrogen `fluoride and containing a substantial amount of organic material, the fiuorine content of the duced substantially.

The hydrogen fluoride sludge used in the process of my invention may be obtained from hydrogen fluoride which has catalyzed the alkylation of an alkylatable parafllnic or naphthenlc hydrocarbon by an olefln or alkyl fluoride or has catalyzed the polymerization of an oleiln.' In such processes the hydrocarbon alkylation or polymerization product forms an upper layer which is separated from the lower layer of used hydrogen fluoride, the latter containing a relatively small quantity of highly unsaturated cyclic organic material dissolved in the hydrogen fluoride or chemically combined with a portion of iti Such used hydrogen fluoride may be subjected to fractional distillation to separate a substantial proportion of the hydrogen fluoride from higher boiling material comprising complexes of hydro- 1 gen uoride with unsaturated hydrocarbons ofv relatively high molecular weight. Because of the manner in which these sludge hydrocarbons are formed, small amounts of these complex organic materials are present in the' products resulting from the alkylation of an isoparalnic hydrocarbon with an olefin or alkyl fluoride. Accordingly, very small amounts', of 4these complex materials may be present in alkylates containing also small amounts of alkyl iluorides which'have heretofore been removed by various treatments' -including extraction by means of liquidhydrogen fluoride. The organicconstituents of hydrogen fluoride sludge present heretofore during such treatment of an alkylate with hydrogen fluoride is small and in normal operation does not exceed a few percent of the liquid volume of the hydrogen fluoride. Now I have found that organically combined fluorine, particularly that present in alkyl fiuorides, is removed from alkylates and other hydrocarbons or hydrocarbon 'mixtures so contaminated, by treatment with hydrogen fluoride in the presence of large amounts of :the

propane fraction is-re'-l ride, I may use also from about 1o to about 90% jthatm'ay be util-ized in deiluorinating a propane by volume of sludge complex and from about 90 to about Dy volume of liquid hydrogen fluo?I ride.

In addition to the hydrocarbons occurring in hydrogen fluoride sludges, other sludge hydrocarferent materials include the hydrocarbons present in sludges formed in hydrocarbon conversions,

particularly alkylation and polymerization re fraction containing ethyl fluoride and recovered from a process in which an isoparaiiin is alkylated bons are also utilizable in my process. These difwith -an olefinic material containing small amounts of ethylene.

By means not illustrated in the drawing,V iSobutanoV and a propane-propylene fraction containing .small amounts of ethylene are directed through line I containing valve 2 to alkylator 3 containing liquid hydrogen fluoride admitted l thereto 'through line I containing valve 5. Al-

kylator 3 is also -provided with suitable cooling orfhea'ting means and also with stlrrer 6 oper- 50 to about 120 C. The process is carried out'v at atmospheric pressure or preferably at a pressure suii'icient to maintain the reaction vmixture y in substantially liquid phase.

The treatment of a hydrocarbon ork hydrocarbon mixture containing fluoride contaminan-ts to kremove uorine therefrom is effected in either batch or continuous types of treatment. In batch type operation one volume of -the hydrocarbon or hydrocarbon mixture contaminated by organic fiuorine compounds is agitated with from about 1.0 to about 2.0 volumes ofthe mixture of liquid hydrogen fluoride and organic constituents of a hydrogen fluoride sludge. This trea-tment is carried out at a temperature of from about 0 to about 150 C., at a pressure sufficient to maintain liquid phase operation,v and for a time generally of from about 0.1 to about 3 hours. The resultant reaction mixture is then separated into treated hydrocarbon material, used hydrogen.

fluoride, and sludge. The former'is washed, dried and distilled or otherwise treated to recover a desired hydrocarbon or hydrocarbon mixture substantially free from organic fluorine compounds, while the used hydrogen fluoride and recovered sludge hydrocarbons are returned to the reactor for further use in treating an additional quantity of the hydrocarbon charging stock.

Continuous treatment of a hydrocarbon containing organically combined fiuorine is eiiected by passing said hydrocarbon and a proportioned amount of hydrogen fluoride and hydrogen fluoride sludge containing organic material through a baflled mixer or other suitable type of contacting equipment in which the hydrocarbon and deuorlnating mixture are contacted at the aforementioned conditions of temperature and pressure for a time sufficient to remove substantially all of the organically combined fluorine from the hydrocarbon material. From this trea'ting equipment the mixture of hydrocarbon material and treating reagent is directed to a separator from which the hydrocarbon layer is rem'oved, washed, dried and distilled or otherwise treated 'to recover the desired hydrocarbons 4substantially free from fiuorine-c-ontaining compounds. The used mixture of hydrogen uoride and vsludge hydrocarbon .mixture is then withdrawn from the separator and at least a por-tion thereof is recycled` to further use in treating an additional quantity of the mentioned charging stock.

In order to illustrate further 'the process of my invention, :the attached diagrammatic drawing is given to indicate one arrangement of equipment Y ated 'by 'prime mover 1. .From alkylator 3 the reaction mixture is directed throughl line '8 containing valve 9 to settler I0 in which the used hydrogen fluoride catalyst separates as a lower layer from the upper hydrocarbon layer, the latter, being then discharged from settler I0 through line II and valve I2 tov charging drum I3, while the used hydrogen fluoride is withdrawn through line I4 containing valve I5 to further treatment and use as hereinafter set forth.

IFrom charging drum I3, the hydrocarbon layer comprising alkylate, unconverted butane fraction; propane, dissolved hydrogen fluoride, and small Vamounts of alkyl iiuorides, particularly ethyl uoride, is directed through line I6 and valve I1 to depropanizer I8 wherein a relatively low boiling mixture comprising essentially propane,'ethylfluoride, and hydrogen fluoride is vaporized and discharged through line I9, valve 20, cooler 2l, line 252, and valve 23 t receiver 24.

The vhigher boiling material comprising alkylate and unconverted butane is discharged from depropanizer I8 through line 25 and valve 2B to further treatment and use not illustrated in the diagrammatic drawing.

In receiver 24. an upper layer comprising essentially propane contaminated with ethyl fluorideisl 4separated from a lower layer comprising essentially liquid hydrogen iluoride, the latter being withdrawn from receiver 24 through line 21 containing valve 20. At least a portion of the used hydrogen fluoride which is discharged through line 21 is recycled therefrom through line 29 and valve 30 to line 4, already mentioned, through which fresh hydrogen fluoride is` introduced to alkylator 3. From receiver 24, the upper layer comprising essentially propane and dissolved ethyl fluoride is passed through line 3| containing valve 32 to contactor 33 provided with stirrer operated by -prime mover 35. In contactor 33 a substantial proportion of the ethyl fluoride -is removed from the upper layer comprising essen- -tially propane by treatment with hydrogen nuoride .sludge hydrocarbons and liquid hydrogen Afluoride directed thereto through line 36 and valve 31 as hereinafter set forth.

Hydrogen fluoride used as catalyst in alkylator v 3 and separated from the hydrocarbon layer in settler I0 is directed .therefrom through line Il, line 38, and valve 39 to fractionator 40 used for regenerating hydrogen fluoride by a. method comprising essentially fractional distillation by which hydrogen iiuorideis separated from relatively high boiling highly unsaturated hydrocarbons also referred to herein as hydrogen iiuoride sludge hydrocarbons. It may be advantageous to employ in fractionator 40 a packing material yof cert-ain metals-such as steel. brass, etc., in the form of rings or some other shape which can be arranged compactly in the fractiona'tor, while at the same time-offering av large surface area. At elevated temperatures, such materials have been shown lines 29 and I, already mentionemto alkylator g I, while the sludge hydrocarbons are discharged from near the bottomof iractionator I through line Il 'containing valve Il. vAt least-a portion. oi' the sludge hydrocarbon-materialis directed-V !rom line Il through line It and valve 31 to conlo tactor u. already mentioned. in, which a hydrocarbon material containing' an alkyl 'fluoride is v deiluorinated in the presence of said 'sludge hydr'ocarbons and also of liquid hydrogen iluoride which is conveniently directed from line 21 15 through line 4I, valve 48, line 3l and valve Il to contactor 33.

The eiiluent from contactor Il is passed through line 41 and valve 4B to .settler from which a lower layer comprising essentially hydrogen iluogo ride and sludge hydrocarbons is directed through line 50 containing valve 5I. A portion of the mixture of hydrogen iluoride and .sludge hydrocarbons being discharged through line ll'is recycled therefrom through line 52 and valve 53 and thence g5 through line and valve 31 to contactor 33, while the remainder of said mixture is directed from line 50 to line 38 and thence to fractionator in which a hydrogen iluoride fraction-containinga high proportion oi' hydrogen fluoride is sep- 30 arated from higher boiling sludge hydrocarbons. From the top of settler 49, the propane fraction, thus substantially freed from ethyl fluoride but containing some dissolved hydrogen iiuoride. is

discharged through line Il and valve 5l into frac- 35 tionator 08y from which a mixture of hydrogen fluoride and .substantially deiluorinated propane is discharged through line 51 and valveV 5l to fur'- J ther treatment or use not illustrated in the dlagrammatic drawing; while a substantially pure 4o propane fraction free from hydrogen fluoride and alkyl iluorides is withdrawn from the bottom. of

fractionator 56 through line 59 and valve Oli.V

Although the foregoing diagrammatic drawing illustrates the manner in which a propane fraction recovered from the alkylation product may be freed from ethyl uoride, it is evident to one skilled in the art that substantially the same form 'oi equipment is also utilizable when it is desired to deuorinate an alkylate or alkylatefraction 60 which contains small amounts of organically combined uorine such-as alkyl uorides.- Thus, an isoparafilnic alkylate suchas that present in admixture with butane and being discharged vfrom depropanizer I8 through line 25 and valve 2B 55 could be debutanized and then subjected to deilu'orination treatment in contactor 33' in the presence of liquid hydrogen fluoride and sludge hydrocarbons. The hydrogen iluoride employed 'with the sludge hydrocarbons could be either sub- 60 stantially anhydrous hydrogen iiuoride-charged c Afrom an outside'source, or it could be regenerated hydrogen fluoride or hydrogen fluoride which has been used in the alkylation process and separated 'from the alkylation products as herein set forth. 35

The following example is given to show results obtained in theoperation of the process, but it is not to be considered to limit unduly the broad scope ofthe invention.

A turbomixer of 1000 cc. capacity was`charged l with 132 grams of used hydrogen iluoride contain- .ing about 40% by weight o'f sludge hydrocarbons, 157 grams of substantially anhydrous hydrogen fluoride, and 102 grams of propane containing 1.2% by weight of fluorine present as ethyl iiuo- Monaca i moval of iluorine.

ride.' These. materials were then contacted in the turbomixer at '25 C. for Zhours -aiterwhich the treated propane was removed therefrom. separated from hydrogen iiuoride. and foundto conV tain 0.27% by weight. of nuorine. The treatment with hydrogen fluoride and sludge hydrocarbons l thus removed 78% oi' the ethyl fluorideirom the propane fraction charged. The deiluorinating ei'- ilciency of the process can be improved by using a higher temperature of treatment and. preferably using a temperature of trom about ,50 to about 120 C. in order'to obtain more complete re- The nature of the present invention and the type of results obtained thereby-are evident from the preceding specification and example. although neither section is to be construed to limit unduly the broad scope of the invention.

I claim as my inventionz. -V

l. A process for treating ahydrocarbon material containingas an impurity a relatively small percentage of organically combined ,fluorine to remove iluorine therefrom which comprises ccntacting said hydrocarbon material at a temperature of from about 0 C. to about 150 C. with a liquid mixture ofv hydrogen fluoride and the organic constituents of a sludge resulting from the treatment of hydrocarbons witha sludge-forxning-hydrocarbon conversion catalyst; said mixture containing from about 40% to about 90% of said organic constituents, and recovering the treated hydrocarbon material. l

2'. A process for treating a hydrocarbon material containing as an impurity a relatively small percentage of organically combined iluorine to remove fiuorine therefrom which comprises contactingsaid hydrocarbon material at a temperaature of from about 0 C.v to about 150 C. with a liquid mixture of hydrogen fluoride and the organic constitutents of.a hydrogen fluoride sludge resulting from the conversion of hydrocarbons in the presence of a hydrogen iluoride catalyst, said mixture containing from about 40% to about 90% of said organic constituents, and recovering the treated hydrocarbon material.

3. A process'for treating a hydrocarbon mate-v,v

rial containing as an impurity a relatively small percentage of organically combined fluorine to removeuorine therefrom which comprises contacting said hydrocarbon material at a temperature of from about 0 C. to about 150 C. with a liquid mixture of hydrogen fluoride and the organic constituents of a hydrogen fluoride sludge resulting from the alkylation of hydrocarbons in the presence of a hydrogen fluoride alkylation catalyst, said mixture containing from about 40% to about of said organic constituents, and recovering the treated hydrocarbon material.

4. The process of claim 2 further characterized in that said contacting step is carried out at a pressure suilcient to maintain the reaction mixture in substantially the liquid phase. 5. The process of claim 2 further :characterized in that from about 1 to about 2 volumes of said liquid mixture are employed in said contacting step per volume of said hydrocarbon material.

6. The process of claim 2 further characterized 1 in that said hydrocarbon material containing the organic fluorine impurity comprises a paramnic product from ahydrogen fluoride catalyzed alkyl- A ation reaction.

ne. 8. vThe process of claim 2 further characterized f 10 in that said hydrocarbon material comprises pro- UNITED STATES PATENTS pane and the organic iiuorine impurity comprises i ethyl fluoride. Number Name Date CARL B. LINN. 2,320,629 Matuszak June 1, v1943 REFERENCES CITED 5- The following references are of record inthe le of this patent: 

